Wiring substrate and method of manufacturing thereof, and thin film transistor and method of manufacturing thereof

ABSTRACT

The invention includes a first step for forming a first conductive layer composed of a high melting point metal to be in contact with an insulating layer; and a second step for forming a second conductive layer by discharging a composition containing a conductive material so as to be in contact with the first conductive layer. The first conductive layer is formed prior to forming the second conductive layer by droplet discharging, and hence, adhesiveness and peel resistance of the second conductive layer are improved. Furthermore, the insulating layer is covered with the first conductive layer, thereby preventing damage or destruction of the insulating layer.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a wiring substrate formed by dropletdischarging and a method of manufacturing thereof. The invention furtherrelates to a thin film transistor and a method of manufacturing thereof.

2. Description of the Related Art

Recently, a droplet discharging technique has been applied to the fieldof a flat panel display, and developed actively. Since a liquid dropletis directly jetted over a substrate, the droplet discharging techniquehas various advantages in that a mask is not required, the technique iseasily applied to a large-size substrate, the material efficiency ishigh, and the like. Accordingly, the droplet discharging technique hasbeen applied to formation of an electrode for a color filter and aplasma display, and the like.

When a wiring substrate is formed by droplet discharging, a compositionincluding particles in nanometer size is used. Since a thin film formedof the above-mentioned composition is not well-adhered to an underlyingthin film, however, the thin film formed of the composition is likely tobe separated from the underlying thin film. Therefore, when the wiringsubstrate including a pattern formed of the composition is subjected toa wet step such as a washing step, which is indispensable for thesemiconductor processing, the pattern is likely to be separated from theunderlying thin film.

Further, when the composition is jetted through an end of a nozzle, aphenomenon, which is called as the Lenard phenomenon, is caused. TheLenard phenomenon is the one in which a jetted composition is chargedpositively due to the deviation of electric charge. Therefore, it hasbeen considered that the thin film adhered with the composition isdamaged or destroyed due to the positively-charged composition.

SUMMARY OF THE INVENTION

In view of the foregoing, it is an object of the present invention toprovide a wiring substrate having improved adhesiveness and peelresistance, and a method of manufacturing the same. Further, it is anobject of the invention to provide a wiring substrate, which can preventdamage or destruction of a thin film adhered with a composition, and amethod of manufacturing the same. Furthermore, it is an object of theinvention to provide a thin film transistor having improved adhesivenessand peel resistance by using the above-mentioned wiring substrate andthe method of manufacturing thereof, and a method of manufacturing thethin film transistor.

In order to overcome the problems set forth above in the related art,the invention provides following countermeasures.

According to one aspect of the invention, a method of manufacturing awiring substrate includes: a first step for forming a first conductivelayer composed of a high melting point metal, which is in contact withan insulating layer; and a second step for discharging a compositioncontaining a conductive material so as to form a second conductive layerwhich is in contact with the first conductive layer. The firstconductive layer is formed prior to forming the second conductive layerby droplet discharging, and hence, the adhesiveness and peel resistanceof the second conductive layer are improved. Further, the insulatinglayer is covered with the first conductive layer, preventing theinsulating layer from being damaged and destroyed.

According to another aspect of the invention, a method of manufacturinga wiring substrate includes: a first step for forming a first conductivelayer composed of a high melting point metal which is in contact with aninsulting layer having an opening; and a second step for discharging acomposition including a conductive material so as to form a secondconductive layer which fills the opening. Accordingly, the adhesivenessand peel resistance of the second conductive layer are improved. Inaddition, the damage or destruction of the insulating layer can beprevented. Furthermore, the first conductive layer functions as abarrier layer to prevent the ingress of impurities from the insulatinglayer.

According to another aspect of the invention, a first conductive layermade from a high melting point metal is interposed between an insulatinglayer and a second conductive layer. The high melting point metal isformed of such material as Ti (titanium); W (tungsten); Cr (chromium);Al (aluminum); Ta (tantalum); Ni (nickel); Zr (zirconium); Hf (hafnium);V (vanadium); Ir (iridium); Nb (niobium); Pd (lead); Pt (platinum); Mo(molybdenum); Co (cobalt); and Rh (rhodium). The first conductive layeris formed by a known method such as sputtering; vapor deposition; ionimplantation; CVD; dipping; and spin coating. Preferably, the firstconductive layer is formed by sputtering, dipping, or spin coating. Whenthe first conducive layer will be insulated later, it is more preferablethat the first conductive layer be formed to have a thickness of from0.01 to 10 nm, and be insulated by natural oxidation.

According to another aspect of the invention, an insulating layer isformed of an oxide material containing silicon or a nitride materialcontaining silicon. This is because a thin film composed of suchmaterials has a preferable dielectric constant etc. in order to serve asa gate insulating film.

According to another aspect of the invention, an insulating layer withan opening is formed of an organic material or a material having askeleton structure, which is composed by bonding silicon and oxygen.Since the organic material has superior flatness, when an electricconductor is formed thereon later, the film thickness of the electricconductor is not extremely thin in a step defference or the electricconductor is not disconnected in a step difference. Therefore, it ispreferable that the insulating layer be formed of the organic material.The organic material further has a low dielectric constant. Accordingly,when an interlayer insulator for a plurality of wirings is formed of theorganic material, wiring capacitance is reduced. Consequently, amultilayer wiring can be formed, which results in high performance andsophisticated function.

As the material having the skeleton structure which is formed by bondingsilicon and oxygen, siloxane polymer can be cited typically. Morespecifically, the siloxane polymer has a skeleton structure formed bybonding silicon and oxygen, and corresponds to a material at leastincluding hydrogen in the substituent or a material at least includingany one of fluorine, alkyl group, aromatic hydrocarbon in thesubstituent. The siloxane polymer is also superior in the flatness, andfurther includes a light transmitting property and a heat resistanceproperty. Therefore, an insulator formed of siloxane polymer can besubjected to a heat treatment at a temperature of from 300 to 600° C. orless. By performing the heat treatment, a hydrogenation treatment and abaking treatment can be carried out, simultaneously.

The insulating layer including an opening is formed with a thickness offrom 100 nm to 2 μm since the opening for connecting a pattern of anupper layer and a pattern of a lower layer is formed in the insulatinglayer.

The second conductive layer is formed of a composition including silver,gold, copper, or indium tin oxide. Molecules of these materials can beprocessed in nanometers size. When nano-size particles are dispersed ina solvent, it is possible to form the second conductive layer easily bydroplet discharging.

The invention further includes a step for insulating a part of the firstconductive layer where is not in contact with the second conductivelayer after the above-mentioned second step. The invention also includesa step for etching a part of the first conductive layer where is not incontact with the second conductive layer. These steps are carried out toprevent a short-circuit of a plurality of elements or wirings, ifnecessary. When the step for insulating the first conductive layer isperformed, it is preferable that the first conductive layer be formedwith a thickness of from 0.01 to 10 nm, and be insulated by naturaloxidation as set forth above.

According to another aspect of the invention, a thin film transistor,which has the second conductive layer completed through theabove-mentioned step as a gate electrode and the insulating layer as agate insulating film, is formed.

According to another aspect of the invention, a wiring substrateincludes: a first conductive layer formed of a high melting point metal,which is in contact with an insulating layer composed of an oxidematerial containing silicon, a nitride material containing silicon, anorganic material, or a material including a skeleton structure with abond of silicon and oxygen; and a second conductive layer composed ofsilver, gold, copper, or indium tin oxide, which is in contact with thefirst conductive layer. Preferably, the first conductive layer is formedto have a thickness of from 0.01 to 10 nm. The high melting point metalis one of Ti, W, Cr, Al, Ta, Ni, Zr, Hf, V, Ir, Nb, Pd, Pt, Mo, Co, orRh. Further, the present invention provides a thin film transistor usingthe insulating layer as a gate insulating film, and the secondconductive layer as a gate electrode. The wring substrate and the thinfilm transistor having the above-described structures are superior inadhesiveness and peel resistance. Therefore, patterns formed over thewring substrate and the thin film transistor are not peeled off even ifthe wiring substrate and the thin film transistor are subjected to a wettreatment.

By using the droplet discharging technique, the adhesiveness and peelresistance of a conductive layer can be improved. Furthermore, thedamage and destruction of an underlying thin film can be preventedaccording to the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

In the accompanying drawings:

FIGS. 1A to 1D are diagrams explaining a method of manufacturing awiring substrate according to the present invention (Embodiment Mode 1);

FIGS. 2A to 2D are diagrams explaining a method of manufacturing awiring substrate according to the invention (Embodiment Mode 2);

FIGS. 3A to 3D are diagrams explaining a method of manufacturing achannel-etched thin film transistor (Embodiment Mode 3);

FIGS. 4A to 4C are diagrams explaining a method of manufacturing achannel protective thin film transistor (Embodiment Mode 3);

FIGS. 5A to 5C are diagrams explaining a method of manufacturing adisplay device (Embodiment Mode 3);

FIGS. 6A to 6D are diagrams explaining a method of manufacturing astaggered thin film transistor (Embodiment Mode 3);

FIGS. 7A and 7B are diagrams explaining a method of manufacturing astaggered thin film transistor and a display device (Embodiment Mode 3);

FIGS. 8A to 8C are diagrams explaining lamination structures of astaggered thin film transistor and a light emitting element, which isconnected to the staggered thin film transistor (Embodiment 2);

FIG. 9A is a top view of a panel which is one embodiment of asemiconductor device according to the present invention, and FIGS. 9Band 9C are cross sectional views thereof (Embodiment 3);

FIG. 10A to 10C are diagrams showing electronic appliances applied withthe present invention (Embodiment 6);

FIGS. 11A to 11C are diagrams showing electronic appliances applied withthe present invention (Embodiment 6);

FIG. 12A is a top view of a panel which is one embodiment of asemiconductor device according to the present invention, and FIG. 12B isa cross sectional view thereof (Embodiment 3);

FIG. 13 is a diagram showing a semiconductor device applied with thepresent invention (Embodiment 4);

FIGS. 14A to 14C are diagrams showing a pixel circuit of a semiconductordevice applied with the present invention (Embodiment 4);

FIGS. 15A to 15E are diagrams showing a protection circuit equipped to asemiconductor device according to the invention (Embodiment 5); and

FIG. 16A is a top view of a pixel circuit of a semiconductor deviceaccording to the invention, and FIG. 16B is an equivalent circuitdiagrams thereof (Embodiment 4).

DETAILED DESCRIPTION OF THE INVENTION Embodiment 1

An embodiment mode of the invention will be described with reference toFIGS. 1A to 1D. A substrate 10 is formed of a glass substrate such as abarium borosilicate glass and alumino borosilicate glass; a quartzsubstrate; a silicon substrate; a metal substrate; a stainlesssubstrate; or a heat-resistant plastic substrate, which can withstandprocessing temperatures of manufacturing steps for the present invention(see FIG. 1A).

An insulating layer 11 is formed on the substrate 10. The insulatinglayer 11 is formed of an oxide material containing silicon or a nitridematerial containing silicon by using a known method such as CVD, plasmaCVD, sputtering, and spin coating so as to have a single layer or alamination layer.

Subsequently, a first conductive layer 12 is formed on the insulatinglayer 11 by using a known method such as sputtering, and vapordeposition. The first conductive layer 12 is formed of a high meltingpoint metal such as Ti, W, Cr, Al, Ta, Ni, Zr, Hf, V, Ir, Nb, Pd, Pt.Mo, Co, and Rh.

When a step for naturally oxidizing the first conductive layer 12 willbe carried out later, the first conductive layer 12 is formed to have afilm thickness of from 0.01 to 10 nm. The first conductive film having0.01 nm in thickness is extremely thin, and therefore, there is apossibility that it does not have a film form. However, the firstconductive layer 12 mentioned here includes a state having no film form.Further, in order to make the first conductive layer 12 thinner, it ispreferably formed by sputtering.

A second conductive layer 13 is then formed by jetting a compositionincluding a conductive material. The second conductive layer 13 isformed by using a droplet discharging means 14. A unit, which has ameans for discharging a liquid droplet such as a nozzle having adischarge port for the composition and a head including one or aplurality of nozzles, is generically referred to as the dropletdischarging means. A diameter of a nozzle for the droplet dischargingmeans 14 is set to from 0.02 to 100 μm (preferably, 30 μm or less). Adischarge amount of the composition jetted through the nozzle is set tofrom 0.001 to 100 pl (preferably, 10 pl or less). The discharge amountis increased in proportion to the diameter of the nozzle. A substrate tobe processed is preferably set as close to the nozzle as possible so asto jet the composition in a predetermined portion. Preferably, thedistance between the substrate and the nozzle is set to about from 0.1to 3.0 mm (preferably, 1 mm or less).

When the composition is jetted from the droplet discharging means 14,the composition tends to be charged positively since deviation ofelectric charge is generated. There is a possibility that the insulatinglayer 11 is damaged due to the positively-charged composition. Since theinsulating layer 11 is covered with the first conductive layer 12 in theinvention, however, the damage or destruction of the insulating layer 11can be prevented.

As for the composition jetted through the discharge port, a material inwhich a conductive material is dissolved or dispersed in a solvent isused. The conductive material corresponds to metal such as Ag, Au, Cu,Ni, Pt, Pd, Ir, Rh, W, and Al; metal sulphide such as Cd, and Zn; oxidesuch as Fe, Ti, Si, Ge, Si, Zr, and Ba; and a microparticle or adispersive nanometer-size particle of silver halide. The conductivematerial further corresponds to indium tin oxide (ITO) used as atransparent conductive film, ITSO composed of indium tin oxide andsilicon oxide, organic indium, organic tin, organic zinc, titaniumnitride, and the like.

Note that, in consideration of the resistivity value, it is preferableto use a material in which any one of gold, silver, and copper isdissolved or dispersed in a solvent as the composition jetted throughthe discharge port. More preferably, silver or copper with lowresistance is used. When silver or copper is used as the composition, abarrier film is additionally provided therewith in order to preventimpurities. As for the solvent, esters such as butyl acetate and ethylacetate; alcohols such as isopropyl alcohol and ethanol; organicsolvents such as methyl ethyl ketone and acetone; and the like can beused. The viscosity of the composition is preferably set to 50 cp orless in order to jet the composition fluently through the discharge portand prevent dryness of the composition. The surface tension of thecomposition is preferably set to 40 mN/m or less. The viscosity and thelike of the composition may be adjusted properly according to a solventto be used and an intended purpose. For example, the viscosity of acomposition in which ITO, organic indium, and organic tin are dissolvedor dispersed in a solvent is preferably set to from 5 to 50 mPa·S; theviscosity of a composition in which silver is dissolved or dispersed ina solvent may be set to from 5 to 20 mPa·S; and the viscosity of acomposition in which gold is dissolved or dispersed in a solvent may beset to from 10 to 20 mPa·S.

Although the diameter of a particle for an electric conductor depends onthe diameter of each nozzle and a predetermined pattern shape, the sizeof the particle for the electric conductor is preferably as small aspossible for the purpose of preventing a clogged nozzle andmanufacturing a high-precise pattern. Preferably, the diameter of theparticle is set to 0.1 μm or less. The composition is formed by a knownmethod such as electrolyzing, atomizing, and wet reducing, and theparticle size thereof is typically about 0.01 to 10 μm. However, in thecase of using a gas evaporation method, each nanometer-size molecularprotected with a dispersing agent is minute and is about 7 nm in size.Further, when each surface of the nanometer-size particles is coveredwith a coating material, the nanometer particles among the solvent arenot aggregated but are uniformly dispersed in the solvent at a roomtemperature, and show a property similar to that of aqueous fluid. As aresult, the coating material is preferably used.

When the step for discharging a composition is performed under reducedpressure, the solvent of the composition is vaporized during a periodfrom discharging the composition till attaching it to an object to beprocessed. Consequently, steps for drying and baking, which should beperformed later, can be both eliminated. It is preferable that the stepfor discharging the composition be performed under reduced pressure soas not to form an oxide film and the like on a surface of the electricconductor. After discharging the composition, one or both of a dryingstep and a baking step is/are performed. Each step for drying and bakingis a step of a heat treatment. For example, the drying is performed for3 minutes at a temperature of 100° C. whereas the baking is performedfor 15 to 30 minutes at temperatures from 200 to 350° C., and thepurposes, temperatures, and time thereof are varied. The steps fordrying and baking are performed at a normal pressure or under reducedpressure by laser beam irradiation, rapid thermal annealing, a heatingfurnace, and the like. Note that the timing of performing the heattreatment is not limited particularly. The substrate may be heated inadvance so as to carry out the steps for drying and baking favorably. Atthis time, the heating temperature depends on a material of thesubstrate and the like, but it is generally set to from 100 to 800° C.(preferably, 200 to 350° C.). According to the steps, the nanometer-sizeparticles are in contact with one another and fusing together and fusingbond are accelerated by hardening and shrinking resin in the peripheryas well as volatilizing the solvent in the composition or removing thedispersing agent chemically.

A continuous wave or pulsed gas laser or solid state laser may be usedfor laser beam irradiation. An excimer laser, a YAG laser, and the likeare cited for the former gas laser, while lasers using crystals such asYAG and YVO₄ doped with Cr, Nd and the like are cited for the lattersolid state laser. Preferably, the continuous wave laser is used inrelation to the absorptance of laser beam. Alternatively, a so-calledhybrid laser irradiation method combining a pulsed oscillation and acontinuous wave may be employed. Note that, the laser beam irradiationfor the heat treatment may be instantaneously performed for severalmicroseconds to several tens seconds so as not to destroy the substrate10 according to heat resistance of the substrate 10.

Rapid thermal annealing (RTA) is performed by instantaneously heatingthe substrate for several microseconds to several minutes while rapidlyraising the temperature with an infrared lamp, a halogen lamp, and thelike that emits ultraviolet light through infrared light in an inert gasatmosphere. This treatment is performed instantaneously, and hence, onlya thin film on the top surface is substantially heated not to adverselyinfluence underlying films. That is, a substrate that is weak in heatresistance such as a plastic substrate is not influenced by the heattreatment.

According to the above-described steps, the insulating layer 11, thefirst conductive layer 12, and the second conductive layer 13 arecompleted. When elements and wirings may be shorted to each other sincethe insulating layer 11 remains coated with the first conductive layer12, any one of two steps as follows should be carried out.

One step is one for forming an insulating layer 16 by insulating a partof the first conductive layer 12 where is not overlapped with the secondconductive layer 13 (see FIG. 1C). Specifically, the part of the firstconductive layer 12 where is not overlapped with the second conductivelayer 13 is oxidized and then insulated. In the case of insulating thefirst conductive layer 12 partly, the first conductive layer 12 ispreferably formed with a thickness of 0.01 to 10 nm such that the partof the first conductive layer is naturally oxidized to become aninsulating layer. As a method of naturally oxidizing the firstconductive layer, a method of exposing to an oxygen atmosphere, and amethod of performing a thermal treatment may be used.

Another step is one for forming a conductive layer 17 by etching thefirst conductive layer 12 while using the second conductive layer 13 asa mask (see FIG. 1D).

The second conductive layer formed above may be used as a wiring. Or,the second conductive layer 13 may be used as a gate electrode and theinsulating layer 11 may be used as a gas insulting film such that theyserve as constituent elements for a thin film transistor. Further, aprotection film may be additionally formed so as to cover the conductivelayer completed through the above-described steps. The protection filmmay be formed of a known material such as an oxide material containingsilicon, and a nitride material containing silicon. Preferably, theprotection film is formed of a silicon nitride film having a dense film.

According to the invention as set forth above, since the firstconductive layer 12 is interposed between the insulating layer 11 andthe second conductive layer 13, which is formed by droplet discharging,the adhesiveness and peel resistance thereof can be improved, therebypreventing the damage and destruction of underlying thin films.

Embodiment Mode 2

Another embodiment mode of the invention will be describe with referenceto FIGS. 2A to 2D. A substrate 20 is formed of a glass substrate, aquartz substrate, and the like (FIG. 2A). An electric conductor(conductor) or a semiconductor 21 is next formed on the substrate 20.The semiconductor 21 is formed on the substrate 20 here by way ofexample. A base film may be formed on the substrate 20 so as to preventintrusion of impurities from the substrate 20, if necessary.

An insulating layer 22 is then formed on the substrate 20. Theinsulating layer 22 is formed to a thickness of from 50 nm to μm(preferably, from 100 nm to 2 μm) by using a known method such as plasmaCVD, sputtering, SOG (spin on glass) method, spin coating, and dropletdischarging. As a material for the insulating layer 22, followingmaterials can be employed: a material containing silicon such as asilicon oxide film, a silicon nitride film, a silicon nitride oxidefilm, and a silicon oxynitride film; an organic material such asacrylic, benzocyclobutene, parylene, flare, and light-transmittingpolyimide; a compound material formed by polymerization of siloxanepolymer etc.; a composition including water-soluble homopolymer andwater-soluble copolymer; and the like.

Since the organic material is superior in the flatness, when an electricconductor is formed later, the film thickness of the electric conductoris not extremely thin or the electric conductor is not disconnected.Therefore, the organic material is favorable. Also, the organic materialis low in the dielectric constant. Accordingly, when the organicmaterial is used as an interlayer insulator for a plurality of wirings,wiring capacitance can be reduced, thereby forming a multilayer wiring.As a result, high performance and sophisticated function can berealized. Note that, in order to prevent degasification, the organicmaterial is preferably sandwiched between thin films composed of aninorganic material including silicon. Concretely, it is preferable thata silicon nitride oxide film, a silicon nitride film, and the like beformed on and under the organic material by plasma CVD or sputtering.

Siloxane polymer is mentioned as a representative example of a materialhaving a skeleton structure formed by bonding silicon and oxygen andincluding at least hydrogen in the substituent, or at least one offluorine, alkyl group, and aromatic hydrocarbon in the substituent.Various materials within the range of the above-mentioned conditions canbe used as substitute for the siloxane polymer. The siloxane polymer issuperior in flatness and heat resistance, and has a light transmittingproperty. After forming an insulator by using siloxane polymer, aheating treatment can be carried out at a temperature of from 300 to600° C. or less. By performing the heat treatment, for instance, ahydrogenation treatment and a baking treatment can be simultaneouslycarried out.

Subsequently, the insulating layer 22 is patterned and processed byphotolithography to form an opening (contact hole) 23. The insulatinglayer may be processed by either dry etching or wet etching. In the caseof using dry etching, an opening 23 having a high aspect ratio (3 ormore) can be formed. Therefore, the dry etching technique is preferablefor forming a multilayer wiring. A mask, which is used in forming theopening 23, may be formed of an organic material such as polyimide, andacrylic by droplet discharging.

The opening 23 may be formed by droplet discharging rather thanphotolithography. In the case of using the droplet dischargingtechnique, the opening is formed by jetting a wet etching solutionthrough a nozzle. It is preferable that a step for properly washing thenozzle with a solvent such as water be added so as to control the aspectratio of the opening 23. Of course, when liquid droplet jetted throughthe nozzle is changed to water or a head filled with a solvent isreplaced, the substrate can be successively processed in a sameapparatus. The successive processing is preferable from the viewpoint ofreduction in processing time. By performing any one of theabove-mentioned methods, the semiconductor 21 formed under theinsulating layer 22 is exposed therefrom after forming the opening 23.

A first conductive layer 24 is formed on the insulating layer 22. Thefirst conductive layer 24 is formed by a known method such assputtering, vapor deposition, and spin coating. The first conductivelayer 24 is formed of a material selected from Ti, W, Cr, Al, Ta, Ni,Zr, Hf, V, Ir, Nb, Pd, Pt, Mo, Co, and Ph.

When a step for naturally oxidizing the first conductive layer 24 iscarried out later, the first conductive layer 24 is formed to have athickness of 0.01 to 10 nm. In the case of forming the first conductivefilm with a thickness of 0.01 nm, since the film thickness thereof isextremely thin, the first conductive layer might not have a thin filmform. However, the first conductive layer 24 includes such the statehaving no thin film form. In order to make the first conductive layer 24thinner, it is preferably formed by sputtering.

The first conductive layer 24 is capable of improving the adhesivenessbetween the insulating layer 22 and a second conductive layer 25, whichwill be formed later as well as functioning as a barrier layer. Thefirst conductive layer 24 is easily embedded, and further makes contactresistance reduced and stabilized. In particular, when the secondconductive layer 25 will be formed of silver or copper later, theformation of the first conductive layer 24 is effective in order toprevent impurities.

Subsequently, the second conductive layer 25 is formed by jetting acomposition including a conductive material. A droplet discharging means26 is used for forming the second conductive layer 25. When thecomposition is jetted from the droplet discharging means 26, thecomposition tends to be charged positively due to the generation ofunbalance of charges. The positive electric charge might destroy theinsulating layer 22. Since the insulating layer 22 is coated with thefirst conductive layer 24, however, it is possible to prevent theinsulating layer 22 from being damaged or destroyed.

According to the above-mentioned steps, the insulating layer 22, thefirst conductive layer 24, and the second conductive layer 25 arecompleted. Note that, in the case where elements or wirings might beshorted to each other since the insulating layer 22 remains covered withthe first conductive layer 24, any one of the following two steps ispreferably carried out.

One step is one for forming an insulating layer 27 by insulating a partof the first conductive layer 24, which is not overlapped with thesecond conductive layer 25 (see FIG. 2C). Specifically, the part of thefirst conductive layer 24 where is not covered with the secondconductive layer 25 is oxidized and then insulated. When the firstconductive layer 24 is insulated in such a manner, it is preferable thatthe first conductive layer 24 be formed to have a thickness of 0.01 to10 nm. Accordingly, the first conducive layer is oxidized naturally tobecome the insulating layer 27. As the method for naturally oxidizingthe first conductive layer, either a method of exposing the conductivelayer to an oxygen atmosphere or a method of performing a heat treatmentmay be used.

Another method is one for forming a conductive layer 28 by etching thepart of the first conductive layer 24 while using the second conductivelayer 25 as a mask (see FIG. 2D).

The second conductive layer formed above may be used as a wiring forconnecting an upper layer and a lower layer. Although not illustrated inthe drawings, a multilayer wiring can be formed by laminating theconductive layers formed according to the present invention. Themultilayer wiring is preferably used for a functional circuit, which isnecessary to be incorporated with a large number of semiconductorelements, such as a CPU. The multilayer wiring allows the semiconductorelements to be highly integrated, which results in drasticminiaturization. Furthermore, since the multilayer wiring is notnecessary to be led out, high-speed fabrication can be realized. Notethat, a protection film may additionally be formed so as to cover theconductive layers completed according to the above-described steps. Theprotection film maybe formed of a known material such as an oxidematerial containing silicon and a nitride material containing silicon.Preferably, a silicon nitride film having dense film quality is employedas the protection film.

According to the invention as set forth above, the first conductivelayer 24 is interposed between the insulating layer 22 and the secondconductive layer 25 formed by droplet discharging, and hence, theadhesiveness and peel resistance of the conductive layer 25 can beimproved. Furthermore, it is possible to prevent thin films under theinsulating layer 22 from being damaged and destroyed. The presentembodiment mode can be implemented by being freely combined with theabove-mentioned embodiment modes.

Embodiment Mode 3

In the present embodiment mode of the invention, a method ofmanufacturing a thin film transistor applied with the preset inventionand a method of manufacturing a display device using the thin filmtransistor will hereinafter be described with reference to FIGS. 3A to3D, FIGS. 4A to 4C, FIGS. 5A to 5C, FIGS. 6A to 6D, and FIGS. 7A and 7B.Firstly, a method of manufacturing a channel-etched thin filmtransistor, in which the present invention is applied to the fabricationof a gate electrode and source and drain wirings, and a method ofmanufacturing a display device using the thin film transistor will beexplained with reference to FIGS. 3A to 3D, and FIG. 5A. Thechannel-etched thin film transistor is a transistor using an amorphoussemiconductor (amorphous silicon (a-Si)) as a channel portion.

On the substrate 200, a conductive layer 201 is formed of a high meltingpoint metal such as Ti, W, Cr, Al, Ta, Ni, Zr, Hf, V, Ir, Nb, Pd, Pt,Mo, Co, and Rh by using a known method (see FIG. 3A). A conductive layer202 functioning as a gate electrode later is formed by jetting acomposition including a conductive material from a droplet dischargingmeans. A part of the conductive layer 201 where is not overlapped withthe conductive layer 202 is insulated to form an insulating layer 219.When a step for naturally oxidizing the conductive layer 201 is carriedout later, the conductive layer 201 is formed to have a thickness of0.01 to 10 nm.

Subsequently, an insulating layer 203 functioning as a gate insulatingfilm, an amorphous semiconductor layer 204, and an n-type amorphoussemiconductor layer 205 are laminated (see FIG. 3B). A mask 206 is nextmade from an insulator such as resist and polyimide. By using the mask206, the amorphous semiconductor layer 204 and the n-type amorphoussemiconductor layer 205 are simultaneously patterned and processed toform an amorphous semiconductor layer 207 and an n-type amorphoussemiconductor layer. After removing the mask 206, conductive layers 210and 211 are formed by discharging a composition including a conductivematerial. While using the conductive layers 210 and 211 as masks, then-type amorphous semiconductor layer is patterned and processed so as toform n-type amorphous semiconductor layers 208 and 209 (see FIG. 3C).Although not illustrated in the drawings, a conductive layer composed ofa high melting point metal may be provided prior to forming theconductive layers 210 and 211. By forming the conductive layer includingthe high melting point metal, the adhesiveness and peel resistance ofthe conductive layers 210 and 211 can be improved.

According to the above-mentioned steps, the channel-etched thin filmtransistor is completed. Next, insulating layers 212, 213, and 214 arelaminated. An opening is then formed in these insulating layers byphotolithography (see FIG. 3D). It is preferable that the insulatinglayer 213 be formed of an organic material or a compound material, whichis formed by polymerization, such as siloxane polymer. When theinsulating layer 213 is formed of the organic material, the insulatinglayers 212 and 214 are preferably formed of thin films made from aninorganic material including silicon in order to prevent degasification.

A conductive layer 215 is then formed of a high melting point metalselected from Ti, W, Cr, Al, Ta, Ni, Zr, Hf, V, Ir, Nb, Pd, Pt, Mo, Co,and Rh on the insulating layer 214. Note that, when a step for naturallyoxidizing the conductive layer 201 will be performed later, theconductive layer 201 is formed to have a thickness of 0.01 to 10 nm. Aconductive layer 225 is next formed by discharging a compositionincluding a conductive material from the droplet discharging means. Apart of the conductive layer 215 where is not overlapped with theconductive layer 225 is insulated to form an insulating layer 216.

Subsequently, conductive layers 217 and 218 are formed by discharging acomposition including a conductive material so as to be in contact withthe conductive layer 225 (see FIG. 5A). The conductive layers 217 and218 are formed of a conductive material having a light transmittingproperty. Concretely, these conductive layers are made from indium tinoxide (ITO), and ITSO formed by mixing ITO and silicon oxide. Aninsulating layer 223, which will serve as a bank, is formed. Anelectroluminescent layer 220 is formed so as to be in contact with theconductive layer 218. A conductive layer 221 and a light shielding layer222 are laminated thereon. Thus, a display device having a displayfunction with use of a light emitting element is completed. In theabove-mentioned structure, the transistor for driving the light emittingelement denotes an n-type transistor, wherein the conductive layer 218serves as a cathode and the conductive layer 221 serves as an anode.Consequently, a display device performing a so-called bottom emission,in which light generated from the light emitting element is emittedtoward the substrate 200, is achieved. In the foregoing manufacturingsteps, the conductive layer 201 and the conductive layer 215 are formedof the high melting point metal respectively prior to forming theconductive layers 202 and 225 by droplet discharging, and therefore, theadhesiveness and peel resistance of the conductive layers 202 and 225can be improved, respectively. As a result, damage and destruction ofthin layers under the conductive layers can be prevented. Note that, theconductive layer 215 also functions as a barrier film.

On the other hand, a method of manufacturing a channel-protective thinfilm transistor, in which the present invention is applied tofabrication of a gate electrode, and a method of manufacturing a displaydevice using the channel-protective thin film transistor will bedescribed with reference to FIGS. 4A to 4C, and FIG. 5B. Thechannel-protective thin film transistor is a transistor using anamorphous semiconductor as a channel portion.

A conductive layer 251 is formed of a high melting point metal on asubstrate 250 (see FIG. 4A). A conductive layer 252, which will serve asa gate electrode later, is formed by discharging a composition includinga conductive material from a droplet discharging means. A part of theconductive layer 251 where is not overlapped with the conductive layer252 is oxidized to form an insulating layer 262. When a step fornaturally oxidizing the conductive layer 201 is performed later, theconductive layer 201 is formed to have a thickness of 0.01 to 10 nm.

Next, an insulating layer 253, which functions as a gate insulatingfilm, an amorphous semiconductor layer 254, an insulating layer 256, andan n-type amorphous semiconductor layer 255 are laminated (see FIG. 4B).The insulating layer 256 may be formed either by photolithography afterforming an insulating film over an entire surface of the substrate or bydroplet discharging. When the photolithography technique is employed,the insulating layer 256 may be formed by exposing the backside to lightwith use of the conductive layer 252, which serves as the gateelectrode. Accordingly, a step for applying resist can be omitted.

A mask 257 is next formed by using an insulator such as resist andpolyimide. By making use of the mask 257, the amorphous semiconductorlayer 254 and the n-type amorphous semiconductor layer 255 aresimultaneously patterned and processed so as to form an amorphoussemiconductor layer 266 and an n-type amorphous semiconductor layer (seeFIG. 4C). Conductive layers 258 and 259 are next formed by discharging acomposition including a conductive material. While using the conductivelayers 258 and 259 as masks, the n-type amorphous semiconductor layer ispatterned to form n-type amorphous semiconductor layers 260 and 261.

According to the above-mentioned steps, the channel-protective thin filmtransistor is completed. Next, a conductive layer 267, which functionsas a pixel electrode, is formed by discharging a composition including aconductive material so as to be in contact with the conductive layer259. An insulating layer 272, which serves as a bank, is formedsuccessively. An electroluminescent layer 270 is formed so as to be incontact with the conductive layer 267, a conductive layer 271 arelaminated thereon, and hence, the display device having a displayfunction with use of a light emitting element is completed (see FIG.5B). In the above-mentioned structure, the transistor for driving thelight emitting element corresponds to the n-type transistor, theconductive layer 267 corresponds to an anode, and the conductive layer271 corresponds to a cathode. Consequently, a display device performinga so-called top emission, in which light generated from the lightemitting element is emitted in the opposite direction of the substrate200, is achieved. According to the foregoing manufacturing steps, sincethe conductive layer 251 is formed prior to fabricating the conductivelayer 252, the adhesiveness and peel resistance of the conductive layer252 can be improved.

FIG. 5C is an equivalent circuit diagram showing structures illustratedin FIGS. 5A and 5B. Specifically, FIG. 5C shows the equivalent circuitdiagram of an n-type driving transistor 230 and a light emitting element231.

Subsequently, a method of manufacturing a staggered thin film transistorin which the present invention is applied to the fabrication of a gateelectrode will be described with reference to FIGS. 6A to 6D. Thestaggered thin film transistor is a transistor using an amorphoussemiconductor as a channel portion.

On a substrate 30, a conductive film 31 is formed of a material such asW, Al, and Ta with a thickness of 100 to 800 nm by a known method ofsputtering, CVD, and the like. An n-type amorphous semiconductor 32 isformed with a thickness of 50 to 200 nm by a known method such as plasmaCVD (see FIG. 6A). Subsequently, masks 33 and 34 are formed of aninsulator such as resist and polyimide. By making use of the masks 33and 34, the conductive film 31 and the n-type amorphous semiconductor 32are simultaneously patterned to form conductive layers 35 and 36, andn-type amorphous semiconductor layers 37 and 38. At this moment, theselayers are formed so as to have tapered shapes as much as possible,respectively. The masks 33 and 34 are then removed by using an ashingapparatus or a stripping apparatus. A semiconductor 40 is formed with athickness of 50 to 200 nm by CVD and the like so as to be in contactwith the n-type amorphous semiconductor layers 37 and 38 (see FIG. 6B).The semiconductor 40 may be formed of an amorphous semiconductor or asemiamorphous semiconductor (hereinafter referred to as SAS), in whichcrystal grains are dispersed in an amorphous semiconductor.

The transistor using the SAS has the electron field-effect mobility of 2to 20 cm²/V·sec, which is 2 to 20 times as large as that of thetransistor using the amorphous semiconductor, and has an intermediatestructure between an amorphous structure and a crystalline structure(including a single crystal and poly crystal). The SAS further includesa third condition that is stable in terms of free energy, and acrystalline structure having short-range order along with latticedistortion. Therefore, the crystal grains having a grain size of from0.5 to 20 nm can be dispersed in the amorphous semiconductor. Further,the SAS is added with hydrogen or halogen of at least 1 atom % or moreas a neutralizing agent for dangling bonds. The more favorable andstable SAS can be obtained by being added with a rare gas element suchas helium, argon, krypton, and neon to promote the lattice distortion.

Subsequently, a mask 39 is formed. By using the mask 39, thesemiconductor 40 is patterned and processed to form a semiconductorlayer 45 (see FIG. 6C). After removing the mask 39, an insulating film41, which serves as a gate insulating film, is formed with a thicknessof 40 to 200 nm by a known method such as CVD. A conductive layer 43 isnext formed with a thickness of 0.5 to 10 nm by a known method such assputtering and CVD. Successively, a conductive layer 44 is formed bydischarging a composition including a conductive material. A baking stepis then carried out, if necessary. A part of the conductive layer 43where is not overlapped with the conductive layer 44 is insulated so asto form an insulating layer 46 (see FIG. 6D).

According to the above-mentioned steps, a thin film transistor iscompleted. In the foregoing steps, since the thin conductive layer 43 isformed prior to forming the conductive layer 44, the adhesiveness andpeel resistance of the conductive layer 44 can be improved.

As depicted in FIGS. 3A to 3D, FIGS. 4A to 4C, and FIGS. 5A to 5C, adisplay element such as a light emitting element and a liquid crystalelement may also be formed at an upper layer of the thin filmtransistor. Therefore, a display device having a display function can becompleted.

Subsequently, a method of manufacturing a top-gate thin film transistor,in which the present invention is applied to the fabrication of a gateelectrode, will be described referring to FIGS. 7A and 7B. The top-gatethin film transistor is a transistor using a polycrystallinesemiconductor as a channel portion.

An amorphous semiconductor is formed on a substrate 300, andcrystallized by using a known crystallization method such as lasercrystallization so as to form a polycrystalline semiconductor. Aninsulating layer 304 is formed on the polycrystalline semiconductor (seeFIG. 7A). An insulating film is preferably formed on the substrate 300as a base film to prevent the ingress of impurities from the substrate300, if necessary. A conductive layer 305 is next formed of a highmelting point metal on the insulating layer 304. When a step fornaturally oxidizing the conductive layer 305 will be carried out later,the conductive layer 305 is formed to have a thickness of 0.01 to 10 nm.A conductive layer 306, which will serve as a gate electrode later, isformed by discharging a composition including a conductive material froma droplet discharging means. A part of the conductive layer 305, whereis exposed from the conductive layer 306, is insulated to form aninsulating layer 320. By making use of the conductive layer 306 as amask, an impurity is doped to the semiconductor such that impurityregions 302 and 303 added with the impurity and a channel formationregion 301 are formed.

An insulating layer 307 is next formed. Openings are formed in theinsulating layer 307 by photolithography. A composition including aconductive material is discharged into the openings to form conductivelayers 308 and 309. A conductive layer 310, which functions as a pixelelectrode, is formed so as to be in contact with the conductive layer308. An orientation film 311 is next formed. Another substrate 316 onwhich a color filter 315, an opposing electrode 314, and an orientationfilm 313 are formed is prepared. The substrate 300 and the substrate 316are adhered to each other with a sealing agent (not illustrated in thedrawings) by thermally curing the sealing agent. A liquid crystal 312 isinjected between the pair of substrates, and hence, a display devicehaving a display function with use of a liquid crystal element iscompleted. Each side of the substrates 316 and 300 is attached withpolarizing plates 317 and 318. According to the above-described steps,the thin conductive layer 305 is formed prior to forming the conductivelayer 306, and therefore, the adhesiveness and peel resistance of theconductive layer 306 can be improved. The present embodiment mode can beimplemented by being freely combined with the foregoing embodimentmodes.

Embodiment 1

The present embodiment explains experimental results for evaluating theadhesiveness of a conductive layer formed according to the presentinvention, and results for measuring the light transmittance of theconductive layer. Firstly, a method of manufacturing twenty-five kindsof samples in total, which are used for respective experiments, will beexplained as follows. Thin titanium (Ti) films are formed on twentyquartz substrates in total by sputtering to have thicknesses of 0.5 nm,1.0 nm, 2.0 nm, and 5.0 nm, respectively. Subsequently, wirings having aline width of 200 μm are formed on the titanium films respectively bydischarging a composition containing silver. Meanwhile, five substrateson which the thin Ti films are not formed are prepared and then wiringshaving a line width of 200 μm are directly formed thereon by dischargingthe composition containing silver. As a first heat treatment, thetwenty-five samples are baked at a temperature of 230° C. for one hour.Thereafter, the twenty samples of the resultant twenty-five samples arebaked under the following different conditions as a second heattreatment: five samples are heated at 250° C. for one hour; five samplesare heated at 300° C. for one hour; five samples are heated at 350° C.for one hour; and five samples are heated at 410° C. for one hour. Notethat, one sample of the twenty-five samples does not have a titaniumfilm and is not subjected to the second heat treatment. Two experimentsof a taping test and another test for a hydrofluoric acid treatment arecarried out on the twenty-five kinds of samples in total formeddescribed above such that the adhesiveness for each sample is evaluated.

The results of the taping test will be explained. The taping test is onefor evaluating the adhesiveness in such a manner that: the middle ofeach wiring composed of the composition containing silver is cut with acutting instrument, a tape is attached firmly to each entire surface ofthe wirings, and then the attached tape is peeled off from the surfacesby a physical means. The evaluation results are shown in Table 1. Asshown in Table 1, in the case of the samples in which no titanium filmis formed, each wiring is peeled off under any temperature conditions.On the other hand, in the case of the samples including the titaniumfilms, each wiring is not peeled off under all temperature conditions.According to the results above, the titanium film is well adhered to thecomposition containing silver. Furthermore, the adhesiveness between thetitanium film and the composition containing silver is favorable evenwhen the titanium films are extremely thin in film thicknesses (0.5 nmand 1.0 nm).

TABLE 1 Temperature for heat treatment none 250° C. 300° C. 350° C. 410°C. Thickness none X X X X X of titanium 0.5 nm ◯ ◯ ◯ ◯ ◯ film 1.0 nm ◯ ◯◯ ◯ ◯ 2.0 nm ◯ ◯ ◯ ◯ ◯ 5.0 nm ◯ ◯ ◯ ◯ ◯ X: the wiring is entirelyremoved. Δ: the wiring is partly removed.

Next, the evaluation results with respect to the test for thehydrofluoric acid treatment will be described. The test for thehydrofluoric acid treatment is carried out as follows: each sample issoaked in hydrofluoric acid, and then the degree of peeling for eachwiring is examined. The hydrofluoric acid treatment is performed for 10seconds. When the wiring is not peeled off, the hydrofluoric acidtreatment for 10 seconds is repeatedly carried out. Table 2 shows theevaluation results thereof. As shown in Table 2, in the case of thesamples including the titanium films, each wiring is not peeled off evenwhen the samples are subjected to the hydrofluoric acid treatments ofnine times, i.e., the hydrofluoric acid treatment for 90 seconds intotal. On the other hand, in the case of the samples including notitanium films, which are heated at 250° C. for one hour as the secondheat treatment, each of the wirings is peeled off after the hydrofluoricacid treatments of eight times, i.e., the hydrofluoric acid treatmentfor 80 seconds in total. Furthermore, in the case of the samplesincluding no titanium films, which are heated at 300° C. for one hour asthe second heat treatment, each of the wirings is peeled off after thehydrofluoric acid treatments of six times, i.e., the hydrofluoric acidtreatment for 60 seconds in total. In accordance with theabove-mentioned results, it is revealed that the adhesiveness betweenthe titanium film and the composition containing silver is favorable.

TABLE 2 Temperature for heat treatment none 250° C. 300° C. 350° C. 410°C. Thickness none ◯ 80 sec 60 sec ◯ ◯ of titanium 0.5 nm ◯ ◯ ◯ ◯ ◯ film1.0 nm ◯ ◯ ◯ ◯ ◯ 2.0 nm ◯ ◯ ◯ ◯ ◯ 5.0 nm ◯ ◯ ◯ ◯ ◯ ◯: the wiring is notremoved after soaking the sample in hydrofluoric acid for 90 seconds.the number of seconds: time for soaking the sample in hydrofluoric aciduntil the wiring is removed.

Although not shown in Table 2, the titanium films are not peeled offeven when the samples including the titanium films are soaked in aremover at a temperature of 80° C. and then soaked in an isopropylalcohol solution for 6 minutes at ambient temperatures. Finally, theresults of measuring the light transmittance will be described.According to the measurement results, the light transmittance of eachsample, on which the titanium films are not formed, is approximately 1.As the thickness of the titanium film is increased, the lighttransmittances tend to be decreased. However, there is not significantdifference in the light transmittances depending on the conditions ofthe heat treatment, and all samples comprise light transmittingproperties.

Embodiment 2

According to the invention, a thin film transistor can be formed, and adisplay device can be formed with use of the thin film transistor. Whena light emitting element is used as a display element and a p-typetransistor is used as a transistor for driving the light emittingelement, light generated from the light emitting element is emittedtoward a bottom surface, toward a top surface, or toward both surfaces.In the present embodiment, lamination structures of the light emittingelement according to any cases of bottom emission, top emission, anddual emission will be described.

The bottom emission, in which light generated from the light emittingelement is emitted toward a substrate 450, is explained referring toFIG. 8A. In this case, source and drain wirings 452 and 453 beingelectrically connected to a transistor 451, an anode 454, anelectroluminescent layer 455, and a cathode 456 are sequentiallylaminated over the substrate 450. A case of the top emission, in whichlight is emitted toward an opposite direction of the substrate 450, isdescribed with reference to FIG. 8B. Source and drain wiring 461 and 462being electrically connected to a transistor 451, an anode 463, anelectroluminescent layer 464, and a cathode 465 are sequentiallylaminated over a substrate 450. According to the structure, even whenlight passes through the anode 463, the light is reflected by the wiring462 so as to be emitted toward the opposite direction of the substrate450. In this structure, the anode 463 is not necessary to be formed of alight-transmitting material. A case of the dual emission, in which lightis emitted both toward the substrate and toward the opposite directionof the substrate, is explained with reference to FIG. 8C. Source anddrain wirings 470 and 471 being electrically connected to a transistor451, an anode 472, an electroluminescent layer 473, and a cathode 474are sequentially laminated over the substrate 450. In this structure,the anode 472 and the cathode 474 are formed of a light-transmittingmaterial or formed with thin film thicknesses, which can transmit light,such that the dual emission can be realized.

In the above-mentioned structures, the cathodes 456, 465, 474 can beformed of a material with low work function. For example, these cathodesare desirably formed of Ca, Al, CaF, MgAg, AlLi, and the like. Theelectroluminescent layers 455, 464, and 473 may have any one of asingle-layer structure, a lamination structure, and a mixed structurehaving no interface between layers. Further, the electroluminescentlayers may be formed of any material such as a singlet material; atriplet material; a material with a combination of the singlet andtriplet materials; an organic material including a low-molecular weightmaterial, a high-molecular weight material, and anintermediate-molecular weight material; an inorganic material typifiedby molybdenum oxide, which is superior in an electron injectingproperty, and the like; and a hybrid material of the organic materialand inorganic material. The anodes 454, 463, 472 are formed of atransparent conductive film, which transmits light. For example, theanodes are formed of a transparent conductive film, in which indiumoxide is mixed with zinc oxide (ZnO) of 2 to 20%, besides ITO, and ITSO.It is preferable that a plasma treatment be carried out under an oxygenatmosphere or a heat treatment be performed under vacuum atmosphereprior to forming the anodes 454, 463, and 472. Partition walls 457, 466,and 475 are formed of a material including silicon, an organic material,or a compound material. When the partition walls are formed of aphotosensitive or nonphotosensitive material such as acrylic andpolyimide, the curvature radius for each side surface thereof is gentlyvaried. Therefore, a thin film formed on each partition wall is notdisconnected. Accordingly, it is preferable that the partition walls beformed of the photosensitive or nonphotosensitive material. The presentinvention can be implemented by being freely combined with theabove-mentioned embodiment modes.

Embodiment 3

An external appearance of a panel which is one embodiment of asemiconductor device according to the invention will be described withreference to FIGS. 9A to 9C. FIG. 9A is a top view of the panel, FIG. 9Bis a cross sectional view taken along a line A-A′ of FIG. 9A, and FIG.9C is a cross sectional view taken along a line B-B′ of FIG. 7A.

As depicted in FIGS. 9A and 9B, a pixel portion 4002, a scanning linedriver circuit 4004, and a protection circuit 4040 are formed over afirst substrate 4001. A sealing agent 4005 is formed so as to surroundthese elements. The first substrate 4001 is sealed with a secondsubstrate 4006 along with a liquid crystal 4007. A signal line drivercircuit 4003 is formed of a polycrystalline semiconductor over anothersubstrate, which is separately prepared. The signal line driver circuit4003 is mounted on the first substrate 4001 at a region other than theregion surrounded by the sealing agent 4005. The pixel portion 4002 andthe scanning line driver circuit 4004 have a plurality of TFTs. FIG. 9Bonly shows a TFT 4010 in the pixel portion 4002 and an element group4041 including a diode and a resistor element in the protection circuit4040. The TFT 4010 uses an amorphous semiconductor as a channel portion.A portion, in which a pixel electrode 4030 being electrically connectedto the TFT 4010, an opposing electrode 4031 formed on the secondsubstrate 4006, and the liquid crystal 4007 are overlapped, correspondsto a liquid crystal element. Orientation films 4020 and 4021 areprovided so as to be in contact with the pixel electrode 4030 and theopposing electrode 4031. A spacer 4035 is provided for the purpose ofcontrolling the distance between the pixel electrode 4030 and theopposing electrode 4031. FIG. 9B shows a TFT 4009 composed of apolycrystalline semiconductor, which is included in the signal linedriver circuit 4003 by way of example. It should be note that severalstructures with respect to the protection circuit 4040 will be describedin more detail in Embodiment 5.

As shown in FIG. 9C, various signals supplied to the signal line drivercircuit 4003 provided separately, the scanning line driver circuit 4004,and the pixel portion 4002 are supplied from a connection terminal 4015.The connection terminal 4015 is connected to an FPC 4018 via ananisotropic conductor 4016. The panel comprises a structure in which thesignal line driver circuit 4003 having the TFT composed of thepolycrystalline semiconductor is attached to the first substrate 4001.Rather than the polycrystalline semiconductor, a driver circuit having aTFT composed of a monocrystalline semiconductor may be adhered to thefirst substrate 4001. Further, a scanning line driver circuit, which isseparately formed over another substrate, may be mounted on the firstsubstrate 4001. Or, only a part of the signal line driver circuit or apart of the scanning line driver circuit may be separately formed onanother substrate, and then mounted on the first substrate. In theabove-mentioned panel, the pixel portion 4002 and the scanning linedriver circuit 4004 are integrated over the substrate 4001. Elementsconstituting such structure preferably use TFTs each of which comprisesa polycrystalline semiconductor or a semiamorphous semiconductor(hereinafter referred to as SAS) as a channel portion. The TFT using theSAS as the channel portion has higher mobility than that of a TFT usingan amorphous semiconductor as a channel portion. Therefore, the TFTusing the SAS as the channel portion sufficiently constitutes thescanning line driver circuit 4004. Although not illustrated in thedrawing, a polarizing plate, a color filter, and a light shielding filmmay additionally be provided to the above-mentioned panel. The case inwhich the liquid crystal element is used as a display element isillustrated in the drawings. However, the present invention may beapplied to a semiconductor device using the other display elements suchas a light emitting element.

Next, another external appearance of a panel which is one embodiment ofa semiconductor device differing to the above-described embodiment, willbe described with reference to FIGS. 12A and 12B. FIG. 12A is a top viewof a panel, and FIG. 12B is a cross sectional view taken along a lineA-A′ of FIG. 12A.

As depicted in FIGS. 12A and 12B, a sealing agent 5006 is provided overa first substrate 5001 so as to surround a pixel portion 5003, anddriver circuits 5004 and 5005. After forming a resin film 5015 on theelements formed over the first substrate 5001, these elements are sealedwith a second substrate 5002. FIG. 12B only exemplifies a CMOS circuit5010 included in a signal line driver circuit 5005; and a TFT 5011 and alight emitting element 5012 included in a pixel portion 5003. Varioussignals supplied to each circuit formed over the first substrate 5001are supplied from a connection terminal 5007.

In the above-mentioned panel, the light emitting element 5012 is sealedwith a glass substrate. The sealing treatment is a treatment forprotecting the light emitting element from moisture. Therefore,following methods can also be used for sealing the light emittingelement: a method for mechanically sealing the light emitting elementwith a cover member; a method for sealing the light emitting elementwith a thermosetting resin or an ultraviolet curable resin; and a methodfor sealing the light emitting element with a thin film having highbarrier function such as metal oxide and metal nitride. As for the covermember, any material such as glass, ceramic, plastic, and metal can beused. When light is emitted toward the cover member side, the covermember should have a light transmitting property. The cover member andthe substrate with the above-mentioned light emitting element formedthereon are adhered to each other with a sealing agent such as athermosetting resin and an ultraviolet curable resin. The sealing agentis cured by a heat treatment or an ultraviolet irradiation treatment soas to form a hermetically enclosed space. It is also effective that ahygroscopic material typified by barium oxide is provided in thehermetically enclosed space. Furthermore, a space between the covermember and the substrate with the light emitting element formed thereoncan be filled with the thermosetting resin or the ultraviolet curableresin. In this case, it is effective that the hygroscopic materialtypified by barium oxide be added into the thermosetting resin or theultraviolet curable resin.

Embodiment 4

A structure of a semiconductor device having a display functionaccording to the present invention will be described with reference toFIG. 13. FIG. 13 is a top view explaining a simple overview of thesemiconductor device, wherein a pixel portion (display portion) 6102,and protection circuits 6103 and 6104 are formed over a substrate 6100.These elements are connected to a driver IC 6107 on a signal line sideand a driver IC 6104 on a scanning line side via a lead wiring. In thecase where an amorphous semiconductor or a microcrystallinesemiconductor is used as an element constituting the pixel portion 6102as illustrated in the drawing, it is preferable that the driver ICs 6107and 6108 be mounted over the substrate by using known technologies suchas COG and TAB, and these driver ICs be used as driver circuits. Whenthe microcrystalline semiconductor is used as an element constitutingthe pixel portion 6102, the driver circuit on the scanning line side maybe composed of the microcrystalline semiconductor whereas the driver IC6107 may be mounted on the signal line side as the driver circuit. As astructure different from the above-mentioned structures, a part of thedriver circuit on the scanning line side and a part of the drivercircuit on the signal line side may be integrated over a same substrateand the driver ICs may be used in place of another parts for the drivercircuit. That is, there are various structures for mounting the driverICs, and the invention may employ any structures.

A pixel circuit of a semiconductor device having a display functionaccording to the invention will hereinafter be described with referenceto FIGS. 14A to 14C. FIG. 14A is an equivalent circuit diagram of apixel 6101. The pixel 6101 comprises a TFT 6110 controlling input of avideo signal into the pixel 6101; a TFT 6111 controlling the amount ofelectric current that flows though a pair of electrodes for a lightemitting element 6113; and a capacitor element 6112 for storinggate-source voltage of the TFT 6111 in a region surrounded by a signalline 6114, power supply lines 6115 and 6117, and a scanning line 6116.Although the capacitor element 6112 is formed in the pixel 6101 in FIG.5B, the present invention is not limited thereto. When a gatecapacitance or the other parasitic capacitance of the TFT 6111 can serveas a capacitor for holding the gate-source voltage, the capacitorelement is not necessarily provided.

FIG. 14B shows a pixel circuit having a structure in which a TFT 6118and a scanning line 6119 are newly added to the structure of the pixel6101 as illustrated in FIG. 14A. By providing the TFT 6118, supply ofthe electric current to the light emitting element 6113 can be forciblystopped. Accordingly, a lighting period can start simultaneously with orimmediately after a writing period starts before signals are writteninto all the pixels. Consequently, the duty ratio is improved. Inparticular, moving images can be displayed favorably in accordance withthe configuration.

FIG. 14C shows a pixel circuit having a structure in which a TFT 6125, aTFT 6126, and a wiring 6127 are newly added to the pixel 6101 asillustrated in FIG. 14B, though the transistor 6111 is removed. In thisstructure, a gate electrode of the TFT 6125 is connected to the wiring6127 storing a constant electric potential such that the electricpotential for the gate electrode is fixed. Further, the TFT 6125 isoperated in a saturation region. The TFT 6126 is connected to the TFT6125 in series and operated in a linear region. A gate electrode of theTFT 6126 is input with video signals for transmitting information aboutlighting or non-lighting of the pixel via the TFT 6110. Since thesource-drain voltage for the TFT 6126 that is operated in the linearregion is low, slight variation in the gate-source voltage of the TFT6126 does not adversely affect the amount of electric current flowingthrough the light emitting element 6113. Accordingly, the amount ofelectric current flowing through the light emitting element 6113 isdetermined by the TFT 6125, which is operated in the saturation region.According to the invention having the above-mentioned structure,luminance fluctuation of the light emitting element 6113, which iscaused by fluctuation in the characteristics of the TFT 6125, can beimproved, thereby enhancing the image quality. It is preferable that thechannel length L₁ and the channel width W₁ for the TFT 6125, and thechannel length L₂ and the channel width W₂ for the TFT6126 be set so asto satisfy the relation of L₁/W₁:L₂/W₂=5 to 6,000:1. It is alsopreferable that the TFTs 6125 and 6126 comprise a same conductivity typefrom the viewpoint of the manufacturing steps. Further, the TFT 6125 maybe either an enhancement TFT or a depletion TFT.

FIG. 16A is a top view of a pixel circuit having the above-mentionedstructure and FIG. 16B is an equivalent circuit diagram thereof. InFIGS. 16A and 16B, TFTs 6700, 6701, and 6702, and a capacitor element6708 are formed in a region surrounded by a signal line 6703, a powersupply line 6704, a scanning line 6705, and another power supply line6706. A pixel electrode 6707 is connected to a source or drain of theTFT 6701.

The display device having the display function of the invention may useeither analog video signals or digital video signals. When the digitalvideo signals are employed, the method of inputting the digital videosignals into the display device is varied depending on the case wherethe video signals use the voltage and the case where the video signalsuse the electric current. That is, luminescence is emitted from thelight emitting element either by inputting the video signals into pixelswith constant voltage or by inputting the video signals into the pixelswith constant current. The method of inputting the video signals withconstant voltage includes the one in which constant voltage is appliedto the light emitting element and the one in which constant currentflows through the light emitting element. Further, the method ofinputting the video signals with constant current includes the one inwhich constant voltage is applied to the light emitting element and theone in which the constant current flows through the light emittingelement. The driving method in which constant voltage is applied to thelight emitting element indicates a constant voltage drive, whereas thedriving method in which constant current flows through the lightemitting element indicates a constant current drive. With respect to theconstant current drive, constant current flows regardless of variationin resistance for the light emitting element. The display device and themethod of driving thereof according to the invention may employ eithervideo signals using voltage or video signals using the electric current.Furthermore, either the constant voltage drive or the constant currentdrive may be used. The present invention can be implemented by beingfreely combined with the above-mentioned embodiment modes andembodiments.

Embodiment 5

An example of a protection circuit included in the semiconductor deviceof the invention will be described. The protection circuit is composedof one or a plurality of elements selected from a TFT, a diode, aresistor element, a capacitance element, and the like. Severalstructures and operation of the protection circuit will hereinafter beexplained. A structure of a protection circuit arranged between anexternal circuit and an internal circuit corresponding to one inputterminal is described with reference to an equivalent circuit diagram ofFIG. 15A. The protection circuit in FIG. 15A comprises p-type TFTs 7220and 7230, capacitor elements 7210 and 7240, and a resistor element 7250.The resistor element 7250 is a resistor with two terminals, wherein oneend of the resistor element is supplied with an input voltage(hereinafter referred to as Vin) and the other end is supplied with alow potential voltage (hereinafter referred to as VSS). The resistorelement 7250 is provided so as to reduce the electric potential of thewiring to VSS when the input terminal is not supplied with the Vin. Theresistance is sufficiently set at a higher value than the wiringresistance of the wiring.

When the Vin is higher than the high potential voltage (hereinafter,referred to as VDD), the TFT 7220 is turned ON and the TFT 7230 isturned OFF in relation to the gate-source voltage. Accordingly, the VDDis supplied to the wiring through the TFT 7220. Therefore, voltagesupplied to the wiring does not exceed the VDD even when the Vin exceedsthe VDD due to noise and the like. On the other hand, when the Vin islower than the VSS, the TFT 7220 is turned OFF and the TFT 7230 isturned ON in relation to the gate-source voltage. Accordingly, the VSSis supplied to the wiring. Therefore, the voltage supplied to the wiringdoes not exceed the VDD even when the Vin becomes lower than the VDD dueto noise and the like. Furthermore, since pulse noise can be dulled inthe voltage supplied from the input terminal because of the capacitorelements 7210 and 7240, a sudden change of voltage due to noise can bereduced to some extent.

According to the arrangement of the protection circuit in the abovestructure, voltage of the wiring is kept in a range between the VSS andthe VDD, and protected from the application of excessively low or highvoltage outside the range. Furthermore, the protection circuit isprovided to the input terminal input with signals such that voltage ofall wirings that is supplied with signals can be kept at a constantlevel (at the VSS in this embodiment) when input of signals is stopped.That is, the protection circuit functions as a short ring, which canmake the wirings short circuits one another when signals are not inputin the input terminal. Therefore, electrostatic damage due to voltagedifference between wirings can be prevented. In addition, when signalsare inputted, the signals supplied to the wiring are not dragged to theVSS since resistance of the resistor element 7250 is at an enough highlevel.

FIG. 15B shows an equivalent circuit diagram of a protection circuit inwhich the p-type TFTs 7220 and 7230 are replaced by diodes 7260 and 7270having rectification. An equivalent circuit diagram in FIG. 15C shows aprotection circuit in which the p-type TFT 7220 and the p-type TFT 7230are replaced by a TFT 7350, a TFT 7360, a TFT 7370, and a TFT 7380. FIG.15D shows a protection circuit having a different structure of the abovestructures, which comprises a resistor element 7280, a resistor element7290, and an n-type TFT 7300. A protection circuit shown in FIG. 15Ecomprises resistor elements 7280 and 7290, a p-type TFT 7310, and ann-type TFT 7320. In each structure of FIGS. 15D and 15E, a wiring andthe like is connected to a terminal 7330. When the electric potential ofthis wiring and the like is changed suddenly, the n-type TFT 7300 or thep-type TFT 7310 and the n-type TFT 7320 are turned ON so that electriccurrent is flown toward a terminal 7340 from the terminal 7330.Accordingly, sudden variation in the electric potential connected to theterminal 7330 is alleviated so that damage or destruction of an elementcan be prevented. The element constituting the above protective circuitis preferably formed of an amorphous semiconductor, which is superior inpressure tightness. This embodiment can be implemented by being freelycombined with the above embodiment modes.

Embodiment 6

Examples for electronic appliances manufactured according to the presentinvention, typically include a digital camera; an audio reproductiondevice such as a car audio; a personal laptop computer; a game machine;a portable information terminal (such as a cellular phone, and aportable game machine); an image reproduction device having a recordingmedium such as a domestic game machine; and the like. Practical examplesthereof are shown in FIGS. 10A to 10C and FIGS. 11A to 11C.

FIG. 10A is a TV set, which comprises a housing 9501, a display portion9502, and the like. FIG. 10B is a monitor for a personal computer, whichcomprises a housing 9601, a display portion 9602, and the like. FIG. 10Cis a personal laptop computer, which comprises a housing 9801, a displayportion 9802, and the like. The present invention is applicable todisplay portions for each electronic appliance. As compared with theportable information terminals, the display portions for theabove-mentioned electronic appliances are larger in size, and therefore,a large-size glass substrate of the so-called fourth generation andfifth generation or later is used. In the present invention, a wiring isformed by the droplet discharging technique, which is superior inmaterial efficiency and is capable of reducing the number ofmanufacturing steps as compared with the case of using the conventionalphotolithography technique. Accordingly, price-reduction can be realizedaccording to the present invention. From the viewpoint of themanufacturing steps and manufacturing costs, it is preferable that thedisplay portions be formed of a transistor using an amorphoussemiconductor and a microcrystalline semiconductor as a channel portion.

FIG. 11A is a cellular phone among the portable information terminals,which comprises a housing 9101, a display portion 9102, and the like.FIG. 11B is a personal digital assistance (PDA) among the portableinformation terminals, which comprises a housing 9201, a display portion9202, and the like. FIG. 11C is a video camera, which comprises displayportions 9701 and 9702, and the like. The present invention isapplicable to the display portions for above-mentioned electronicappliances. Since the above-mentioned electronic appliances are portableterminals, each screen thereof is relatively small in size. Accordingly,display portions for the portable information terminals are preferablyminiaturized by mounting a driver circuit using a thin film transistor,which employs a polycrystalline semiconductor as a channel, a functioncircuit such as a CPU, and a multilayer wiring over a same substrate asa display portion. At this moment, when a wiring is formed by dropletdischarging, which is capable of reducing the number of processingsteps, according to the invention, price-reduction can be realized.Furthermore, since each electronic appliance mentioned above is aportable information terminal, a display portion using a light emittingelement is preferably employed so as to increase added value in terms ofthinness, lightness, and miniaturization. The present embodiment can beimplemented by being freely combined with the above-mentioned embodimentmodes and embodiments.

The present invention has been fully described by way of embodimentmodes and embodiments with reference to the accompanying drawings. As iswell known to those skilled in the art, the present invention can beembodied in several forms, and the embodiment modes and its details canbe changed and modified without departing from the purpose and scope ofthe present invention. Accordingly, interpretation of the presentinvention should not be limited to descriptions mentioned in theforegoing embodiment modes and embodiments. Note that in the structuresaccording to the present invention described above, portions identicalto each other are denoted by same reference numerals in the accompanyingdrawings.

1. A method of manufacturing a wiring substrate, comprising forming afirst conductive layer including a high melting point metal so as to bein contact with an insulating layer; forming a second conductive layerso as to be partly in contact with the first conductive layer byselectively discharging a composition containing a conductive material;and insulating a part of the first conductive layer which is not incontact with the second conductive layer.
 2. A method according to claim1, wherein the insulating layer is formed of an oxide materialcontaining silicon or a nitride material containing silicon.
 3. A methodaccording to claim 1, wherein the first conductive layer is formed tohave a thickness of from 0.01 to 10 nm.
 4. A method according to claim1, wherein the high melting point metal comprises a material selectedfrom the group consisting of Ti (titanium); W (tungsten); Cr (chromium);Al (aluminum); Ta (tantalum); Ni (nickel); Zr (zirconium); Hf (hafnium);V (vanadium); Ir (iridium); Nb (niobium); Pd (lead); Pt (platinum); Mo(molybdenum); Co (cobalt); and Rh (rhodium).
 5. A method according toclaim 1, wherein the first conductive layer is formed by sputtering,dipping, or spin coating.
 6. A method according to claim 1, wherein thecomposition comprises a material selected from the group consisting ofsilver, gold, copper, and indium tin oxide.
 7. A method according toclaim 1, wherein a thin film transistor is formed by using theinsulating layer as a gate insulating film and using the secondconductive film as a gate electrode.
 8. A method of manufacturing awiring substrate, comprising: forming a first conductive layer includinga high melting point metal so as to be in contact with an insulatinglayer; forming a second conductive layer so as to be partly in contactwith the first conductive layer by selectively discharging a compositioncontaining a conductive material; and etching a part of the firstconductive layer which is not in contact with the second conductivelayer.
 9. A method according to claim 8, wherein the insulating layer isformed of an oxide material containing silicon or a nitride materialcontaining silicon.
 10. A method according to claim 8, wherein the firstconductive layer is formed to have a thickness of from 0.01 to 10 nm.11. A method according to claim 8, wherein the high melting point metalcomprises a material selected from the group consisting of Ti(titanium); W (tungsten); Cr (chromium); Al (aluminum); Ta (tantalum);Ni (nickel); Zr (zirconium); Hf (hafnium); V (vanadium); Ir (iridium);Nb (niobium); Pd (lead); Pt (platinum); Mo (molybdenum); Co (cobalt);and Rh (rhodium).
 12. A method according to claim 8, wherein the firstconductive layer is formed by sputtering, dipping, or spin coating. 13.A method according to claim 8, wherein the composition comprises amaterial selected from the group consisting of silver, gold, copper, andindium tin oxide.
 14. A method according to claim 8, wherein a thin filmtransistor is formed by using the insulating layer as a gate insulatingfilm and using the second conductive film as a gate electrode.
 15. Amethod of manufacturing a wiring substrate, comprising: forming a firstconductive layer including a high melting point metal so as to be incontact with an insulating layer provided with an opening; forming asecond conductive layer while filling the opening by selectivelydischarging a composition containing a conductive material; andinsulating a part of the first conductive layer which is not in contactwith the second conductive layer.
 16. A method according to claim 15,wherein the first conductive layer is formed to have a thickness of from0.01 to 10 nm.
 17. A method according to claim 15, wherein the highmelting point metal comprises a material selected from the groupconsisting of Ti (titanium); W (tungsten); Cr (chromium); Al (aluminum);Ta (tantalum); Ni (nickel); Zr (zirconium); Hf (hafnium); V (vanadium);Ir (iridium); Nb (niobium); Pd (lead); Pt (platinum); Mo (molybdenum);Co (cobalt); and Rh (rhodium).
 18. A method according to claim 15,wherein the first conductive layer is formed by sputtering, dipping, orspin coating.
 19. A method according to claim 15, wherein thecomposition comprises a material selected from the group consisting ofsilver, gold, copper, and indium tin oxide.
 20. A method according toclaim 15, wherein a thin film transistor is formed by using theinsulating layer as a gate insulating film and using the secondconductive film as a gate electrode.
 21. A method according to claim 15,wherein the insulating layer comprises a material selected from thegroup consisting of an organic material and a material having a skeletonstructure formed by bonding silicon and oxygen.
 22. A method accordingto claim 15, wherein the insulating layer is formed to have a thicknessof from 100 nm to 2 μm.
 23. A method of manufacturing a wiringsubstrate, comprising: forming a first conductive layer including a highmelting point metal so as to be in contact with an insulating layerprovided with an opening; forming a second conductive layer whilefilling the opening by selectively discharging a composition containinga conductive material; and etching a part of the first conductive layerwhich is not in contact with the second conductive layer.
 24. A methodaccording to claim 23, wherein the first conductive layer is formed tohave a thickness of from 0.01 to 10 nm.
 25. A method according to claim23, wherein the high melting point metal comprises a material selectedfrom the group consisting of Ti (titanium); W (tungsten); Cr (chromium);Al (aluminum); Ta (tantalum); Ni (nickel); Zr (zirconium); Hf (hafnium);V (vanadium); Ir (iridium); Nb (niobium); Pd (lead); Pt (platinum); Mo(molybdenum); Co (cobalt); and Rh (rhodium).
 26. A method according toclaim 23, wherein the first conductive layer is formed by sputtering,dipping, or spin coating.
 27. A method according to claim 23, whereinthe composition comprises a material selected from the group consistingof silver, gold, copper, and indium tin oxide.
 28. A method according toclaim 23, wherein a thin film transistor is formed by using theinsulating layer as a gate insulating film and using the secondconductive film as a gate electrode.
 29. A method according to claim 23,wherein the insulating layer comprises a material selected from thegroup consisting of an organic material and a material having a skeletonstructure formed by bonding silicon and oxygen.
 30. A method accordingto claim 23, wherein the insulating layer is formed to have a thicknessof from 100 nm to 2 μm.
 31. A method of manufacturing a wiringsubstrate, comprising: forming a first conductive layer including a highmelting point metal so as to be in contact with an insulating layer;forming a second conductive layer on an upper surface of a first part ofthe first conductive layer by selectively discharging a compositioncontaining a conductive material; and insulating a second part of thefirst conductive layer with the second conductive layer provided on theupper surface of the first part of the first conductive layer.
 32. Amethod according to claim 31, wherein the first conductive layer isformed to have a thickness of from 0.01 to 10 nm.
 33. A method accordingto claim 31, wherein the high melting point metal comprises a materialselected from the group consisting of Ti (titanium); W (tungsten); Cr(chromium); Al (aluminum); Ta (tantalum); Ni (nickel); Zr (zirconium);Hf (hafnium); V (vanadium); Ir (iridium); Nb (niobium); Pd (lead); Pt(platinum); Mo (molybdenum); Co (cobalt); and Rh (rhodium).
 34. A methodaccording to claim 31, wherein the composition comprises a materialselected from the group consisting of silver, gold, copper, and indiumtin oxide.
 35. A method of manufacturing a wiring substrate, comprising:forming a first conductive layer including a high melting point metal soas to be in contact with an insulating layer; forming a secondconductive layer on an upper surface of a first part of the firstconductive layer by selectively discharging a composition containing aconductive material; and etching a second part of the first conductivelayer using the second conductive layer as a mask.
 36. A methodaccording to claim 35, wherein the first conductive layer is formed tohave a thickness of from 0.01 to 10 nm.
 37. A method according to claim35, wherein the high melting point metal comprises a material selectedfrom the group consisting of Ti (titanium); W (tungsten); Cr (chromium);Al (aluminum); Ta (tantalum); Ni (nickel); Zr (zirconium); Hf (hafnium);V (vanadium); Ir (iridium); Nb (niobium); Pd (lead); Pt (platinum); Mo(molybdenum); Co (cobalt); and Rh (rhodium).
 38. A method according toclaim 35, wherein the composition comprises a material selected from thegroup consisting of silver, gold, copper, and indium tin oxide.